US5162487A - Melamine resin moldings having increased elasticity - Google Patents

Melamine resin moldings having increased elasticity Download PDF

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Publication number
US5162487A
US5162487A US07/744,244 US74424491A US5162487A US 5162487 A US5162487 A US 5162487A US 74424491 A US74424491 A US 74424491A US 5162487 A US5162487 A US 5162487A
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melamine
sub
substituted
fibers
mol
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US07/744,244
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Juergen Weiser
Wolfgang Reuther
Gerhard Turznik
Wolfgang Fath
Heinz Berbner
Onno Graalmann
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BASF SE
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BASF SE
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Priority claimed from DE3922733A external-priority patent/DE3922733A1/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/141Hydrocarbons
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G12/00Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/26Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C08G12/30Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with substituted triazines
    • C08G12/32Melamines
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G12/00Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/40Chemically modified polycondensates
    • C08G12/42Chemically modified polycondensates by etherifying
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/94Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2361/00Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2361/20Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08J2361/26Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C08J2361/28Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine

Definitions

  • the present invention relates to melamine/formaldehyde condensation resin moldings, in particular foams and fibers, having increased elasticity, in which some of the melamine has been replaced by substituted melamine.
  • DE-A-2,915,457 describes melamine/formaldehyde condensation resin foams in which some or all of the melamine may be replaced by alkyl-substituted melamine. Replacement by hydroxyoxaalkylmelaxlnes is not disclosed.
  • EP-A-221,330 describes melamine/formaldehyde condensation resin moldings, preferably foams and fibers, in which from 1 to 80% by weight of the melamine has been replaced by hydroxyalkylaminemelamine. The addition increases the strength, but reduces the elasticity.
  • the present invention accordingly provides moldings, preferably foams and fibers, based on melamine/formaldehyde condensation products in which from 0.1 to 70 mol % of the melamine has been replaced by melamine substituted by from 1 to 3 hydroxyoxaalkyl groups of the formula
  • the melamine/formaldehyde condensation products which are suitable for the production of the moldings are known and described, for example, in DE-A-2,915,457.
  • the melamine:formaldehyde molar ratio may vary within broad limits of from 1:1.5 to 1:4.5, preferably from 1:2.5 to 1:3.5.
  • the essential feature of the present invention is the use of hydroxyoxaalkylmelamines. These substances and their preparation are disclosed in EP-A-225,433. These compounds are melamines which carry from 1 to 3 groups of the formula
  • hydroxyoxaalkylmelamines have an unlimited shelf life in aqueous solution.
  • from 0.1 to 70 mol % of the melamine in the known melamine/formaldehyde condensation products are replaced by hydroxyoxaalkylmelamines.
  • Fibers are expediently produced using from 1 to 70, preferably 2 to 50 and in particular 5 to 25 mol % of the substituted melamine.
  • Foams are expediently produced using from 0.1 to 50, preferably 0.5 to 30 and in particular 1 to 15 mol % of the substituted melamine.
  • the resins generally have a melamine component formaldehyde molar ratio of from 1:1.5 to 1:4.5, preferably 1:2.5 to 1:3.5. They may also contain small amounts of customary additives, such as disulfite, formide, citrate, phosphate, polyphosphate, urea, dicyandiamide or cyanamide. Moldings are produced by curing the resins in a conventional manner by adding small amounts of acids, preferably formic acid
  • Foams can be produced by foaming an aqueous solution or dispersion containing the melamine/formaldehyde precondensate modified according to the invention, an emulsifier, a blowing agent and a curing agent, and also, if desired, customary additives, and subsequently curing the foam.
  • the melamine/formaldehye resin modified according to the invention is spun in a heated atmosphere in a manner known per se after addition of a curing agent and at the same time the solvent (H 2 O) is evaporated and the condensate is cured.
  • a process of this type is described in detail in DE-A-2,364,091.
  • the fibers obtained have increased elongation and low sliding friction.
  • the elongation at break of the HOM fibers is 30% (cf. HEM 15%).
  • the sliding friction test gave a coefficient of 0.65 (HEM 0.9) at a speed of 2 mm/s.
  • the foamable mixture obtained in this way is foamed at 120 degrees in a microwave oven with irradiation by microwave energy and cured Hot air at 250 degrees is subsequently passed through the crude foam for 30 minutes.
  • the final foam has a density of 12 kg/m: 17% of the melamine has been replaced by hydroxyoxapentyl-melamine.
  • the elongation at break (DIN 53 455) is increased by 25%.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

Moldings, in particular foams and fibers, based on melamine/formaldehyde condensation products, in which from 0.1 to 70 mol % of the melamine have been replaced by melamine substituted by from 1 to 3 hydroxyoxaalkyl groups of the formula
--(CH.sub.2 --CH.sub.2 --O).sub.n --CH.sub.2 --CH.sub.2 --OH
n=1-5)
have increased elasticity.

Description

This is a division of application Ser. No. 07/550,992, filed on Jul. 11, 1990.
The present invention relates to melamine/formaldehyde condensation resin moldings, in particular foams and fibers, having increased elasticity, in which some of the melamine has been replaced by substituted melamine.
Melamine resin foams and fibers have been disclosed, for example, in DE-A-2,915,457 and DE-A-2,364,091. It is an object of the present invention to improve the elasticity of moldings of this type.
DE-A-2,915,457 describes melamine/formaldehyde condensation resin foams in which some or all of the melamine may be replaced by alkyl-substituted melamine. Replacement by hydroxyoxaalkylmelaxlnes is not disclosed.
EP-A-221,330 describes melamine/formaldehyde condensation resin moldings, preferably foams and fibers, in which from 1 to 80% by weight of the melamine has been replaced by hydroxyalkylaminemelamine. The addition increases the strength, but reduces the elasticity.
We have found that the abovementioned object is achieved by replacing from 1 to 70 mol % of the melamine in the melamine/formaldehyde condensation resins by a melamine substituted by from 1 to 3 hydroxyoxaalkyl groups.
The present invention accordingly provides moldings, preferably foams and fibers, based on melamine/formaldehyde condensation products in which from 0.1 to 70 mol % of the melamine has been replaced by melamine substituted by from 1 to 3 hydroxyoxaalkyl groups of the formula
--(CH.sub.2 --CH.sub.2 --O).sub.n --CH.sub.2 --CH.sub.2 --OH
(n=1-5).
The melamine/formaldehyde condensation products which are suitable for the production of the moldings are known and described, for example, in DE-A-2,915,457. The melamine:formaldehyde molar ratio may vary within broad limits of from 1:1.5 to 1:4.5, preferably from 1:2.5 to 1:3.5.
The essential feature of the present invention is the use of hydroxyoxaalkylmelamines. These substances and their preparation are disclosed in EP-A-225,433. These compounds are melamines which carry from 1 to 3 groups of the formula
--(CH.sub.2 --CH.sub.2 --O).sub.n --CH.sub.2 --CH.sub.2 --OH
(n=1-5)
in particular the 5-hydroxy-3-oxapentyl group N-Mono-, N,N'-bis- and N,N',N"-tris(5-hydroxy-3-oxapentyl)melamine is particularly suitable A mixture of these three compounds is preferably employed, for example in the molar ratio 1:0.5 to 10:0.5 to 10. In contrast to hydroxyethylmelamines, hydroxyoxaalkylmelamines have an unlimited shelf life in aqueous solution. In the invention, from 0.1 to 70 mol % of the melamine in the known melamine/formaldehyde condensation products are replaced by hydroxyoxaalkylmelamines.
Fibers are expediently produced using from 1 to 70, preferably 2 to 50 and in particular 5 to 25 mol % of the substituted melamine.
Foams are expediently produced using from 0.1 to 50, preferably 0.5 to 30 and in particular 1 to 15 mol % of the substituted melamine.
To prepare the resins, melamine and substituted melamine are polycondensed together with formaldehyie. However, it is also possible to start from mixtures of the individual condensation products with formaldehye or to subsequently add further (substituted) melamine to one of the condensation products The resins generally have a melamine component formaldehyde molar ratio of from 1:1.5 to 1:4.5, preferably 1:2.5 to 1:3.5. They may also contain small amounts of customary additives, such as disulfite, formide, citrate, phosphate, polyphosphate, urea, dicyandiamide or cyanamide. Moldings are produced by curing the resins in a conventional manner by adding small amounts of acids, preferably formic acid
Foams can be produced by foaming an aqueous solution or dispersion containing the melamine/formaldehyde precondensate modified according to the invention, an emulsifier, a blowing agent and a curing agent, and also, if desired, customary additives, and subsequently curing the foam. It has become apparent that particularly elastic foams are obtained if relatively highly concentrated, preferably 68 percent strength by weight or more and in particular 72 percent strength by weight or more solutions or dispersions are employed (the concentrations being based on the resin/water mixture without additives) and if foaming is carried out under conditions such that initially only a slight increase in viscosity occurs, and the curing, with a considerable increase in viscosity, only commences when the foaming is substantially complete. A process of this type is described in detail in DE-A-2,915,457. The foams obtained have increased elasticity, elongation at break and tensile strength.
In order to produce fibers, the melamine/formaldehye resin modified according to the invention is spun in a heated atmosphere in a manner known per se after addition of a curing agent and at the same time the solvent (H2 O) is evaporated and the condensate is cured. A process of this type is described in detail in DE-A-2,364,091. The fibers obtained have increased elongation and low sliding friction.
EXAMPLE 1 Melamine Resin Containing 10 mol % of Substituted Melamine
114 g of formaldehyde (40%), 160 g of melamine, 70 g of paraformaldehye, 58 g of 80% hydroxyoxapentylmelamine (mono:bis tris =1:5:4), 9 g of sodium disulfite and 11 g of dicyandiamide are heated to 95° C. As soon as a clear solution forms, the pH is adjusted to 8. The mixture is kept at 95° C. until a viscosity of 350 Pas is reached. After rapid cooling, a resin having a final viscosity of 380 Pas is obtained.
Production of Fibers and Physical Data
2% of formic acid (35%) are added to the above-described resin, which is mixed to form a homogeneous material and fed to a centrifugal spinning apparatus. Fibers having a diameter of from 5 to 15 μm are obtained. The final strength is achieved by conditioning (200° C., 10 min).
The elongation at break of the HOM fibers is 30% (cf. HEM 15%). The sliding friction test gave a coefficient of 0.65 (HEM 0.9) at a speed of 2 mm/s.
EXAMPLE 2 Melamine Resin Containing 3 mol % of Substituted Melamine
20 g of a mixture of N-mono-, N,N'-bis- and N,N',N"-trishydroxyoxapentylmelamine in the molar ratio 1:5.4 is dissolved in 80 g of water. This solution has a shelf life of significantly longer than 6 months.
50 g of this solution are mixed with stirring at room temperature with 200 g of a spray-dried, sulfite-containing melamine/formaldehyde resin (molar ratio 1:3) and 51 g of water, in which 2 g of sodium formate and 4 g of sodium citrate are dissolved, to form a homogeneous mixture
Production of Foams and Physical Data
A mixture of 5 g of water, 4.5 g of the sodium salt of C-15 paraffinsulfonic acid (as a 40% strength solution) and 2.7 g of the sodium salt of a sulfated C-16/C-18 alfol (as a 50% strength solution) which has been reacted with 80 mol of ethylene oxide, 7.0 g of formic acid (75%) and 50 g of pentane is incorporated into the above-described resin solution to form a homogeneous mixture.
The foamable mixture obtained in this way is foamed at 120 degrees in a microwave oven with irradiation by microwave energy and cured Hot air at 250 degrees is subsequently passed through the crude foam for 30 minutes. The final foam has a density of 12 kg/m: 17% of the melamine has been replaced by hydroxyoxapentyl-melamine.
Compared with a foam produced without the addition according to the invention, the elongation at break (DIN 53 455) is increased by 25%.

Claims (3)

We claim:
1. A fiber molding based on a melamine/formaldehyde condensation product, in which from 0.1 to 70 mol % of the melamine has been replaced by melamine substituted by from 1 to 3 hydroxyoxaalkyl groups of the formula
--(CH.sub.2 --CH.sub.2 --().sub.n --CH.sub.2 --CH.sub.2 --OH
(n=1-5).
2. A molding as claimed in claim 1, wherein the hydroxyoxaalkyl group is the 5-hydroxy-3-oxapentyl group.
3. A molding as claimed in claim 1, wherein the substituted melamine is a mixture of N-mono-, N,N'-bis and N,N',N"-tris(5-hydroxy-3-oxapentyl)melamine.
US07/744,244 1989-07-11 1991-08-13 Melamine resin moldings having increased elasticity Expired - Lifetime US5162487A (en)

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Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE3922733A DE3922733A1 (en) 1989-07-11 1989-07-11 MELAMINE RESIN MOLDED BODY WITH INCREASED ELASTICITY
DE3922733 1989-07-11
US07/744,244 US5162487A (en) 1989-07-11 1991-08-13 Melamine resin moldings having increased elasticity

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5837013A (en) * 1994-12-23 1998-11-17 Basf Aktiengesellschaft Preparation of colored melamine-formaldehyde condensation products
US5916999A (en) * 1996-04-22 1999-06-29 Basf Aktiengesellschaft Process for producing filaments from melamine/formaldehyde condensation products
US6297178B1 (en) 1996-05-02 2001-10-02 Basf Aktiengesellschaft Flameproof fabrics based on melamine resin fibres
US20040054034A1 (en) * 2000-12-15 2004-03-18 Manfred Ratzsch Polymer-modified inorganic particles
US20040219852A1 (en) * 2001-07-16 2004-11-04 Hans-Dieter Eichhorn Flameproof textile surface structures
US20050020750A1 (en) * 2000-12-15 2005-01-27 Manfred Ratzsch Method for curing aminoplast resins
US20050038226A1 (en) * 2001-11-19 2005-02-17 Manfred Ratzsch Products, especially moulding materials of polymers containing triazine segments, method for the production thereof and uses of the same
US20060021148A1 (en) * 2004-07-30 2006-02-02 Weller David E Jr Fiberglass products for reducing the flammability of mattresses
US7012108B2 (en) 2000-12-15 2006-03-14 Agrolinz Melamin Gmbh Modified inorganic particles
US20060068675A1 (en) * 2004-09-01 2006-03-30 Handermann Alan C Wet-lay flame barrier
US20060160454A1 (en) * 2005-01-13 2006-07-20 Handermann Alan C Slickened or siliconized flame resistant fiber blends
US20070267609A1 (en) * 2003-07-22 2007-11-22 Ami Agrolinz Melamine International Gmbh Composite Materials Comprising Plastics and Wood
CN101735555B (en) * 2009-12-22 2011-11-16 四川大学 High-flexibility melamino-formaldehyde foam material and preparation method thereof
CN103665755A (en) * 2013-11-28 2014-03-26 南通紫鑫实业有限公司 Preparation methods of melamino-formaldehyde resin for foam and melamino-formaldehyde resin foam

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4996289A (en) * 1988-08-25 1991-02-26 Basf Aktiengesellschaft Continuous preparation of aqueous melamine/formaldehyde precondensate solutions

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4996289A (en) * 1988-08-25 1991-02-26 Basf Aktiengesellschaft Continuous preparation of aqueous melamine/formaldehyde precondensate solutions

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5837013A (en) * 1994-12-23 1998-11-17 Basf Aktiengesellschaft Preparation of colored melamine-formaldehyde condensation products
US5916999A (en) * 1996-04-22 1999-06-29 Basf Aktiengesellschaft Process for producing filaments from melamine/formaldehyde condensation products
US6297178B1 (en) 1996-05-02 2001-10-02 Basf Aktiengesellschaft Flameproof fabrics based on melamine resin fibres
US20040054034A1 (en) * 2000-12-15 2004-03-18 Manfred Ratzsch Polymer-modified inorganic particles
US20050020750A1 (en) * 2000-12-15 2005-01-27 Manfred Ratzsch Method for curing aminoplast resins
US7208540B2 (en) 2000-12-15 2007-04-24 Agrolinz Melamin Gmbh Process for curing aminoplast resins
US7196131B2 (en) 2000-12-15 2007-03-27 Agrolinz Melamin Gmbh Polymer-modified inorganic particles
US7012108B2 (en) 2000-12-15 2006-03-14 Agrolinz Melamin Gmbh Modified inorganic particles
US20040219852A1 (en) * 2001-07-16 2004-11-04 Hans-Dieter Eichhorn Flameproof textile surface structures
US20050038226A1 (en) * 2001-11-19 2005-02-17 Manfred Ratzsch Products, especially moulding materials of polymers containing triazine segments, method for the production thereof and uses of the same
US7173104B2 (en) 2001-11-19 2007-02-06 Ami - Agrolinz Melamine International Gmbh Products, especially moulding materials of polymers containing triazine segments, method for the production thereof and uses of the same
US20070267609A1 (en) * 2003-07-22 2007-11-22 Ami Agrolinz Melamine International Gmbh Composite Materials Comprising Plastics and Wood
US20060021148A1 (en) * 2004-07-30 2006-02-02 Weller David E Jr Fiberglass products for reducing the flammability of mattresses
US8163664B2 (en) 2004-07-30 2012-04-24 Owens Corning Intellectual Capital, Llc Fiberglass products for reducing the flammability of mattresses
US20060068675A1 (en) * 2004-09-01 2006-03-30 Handermann Alan C Wet-lay flame barrier
US20060160454A1 (en) * 2005-01-13 2006-07-20 Handermann Alan C Slickened or siliconized flame resistant fiber blends
US7589037B2 (en) 2005-01-13 2009-09-15 Basofil Fibers, Llc Slickened or siliconized flame resistant fiber blends
CN101735555B (en) * 2009-12-22 2011-11-16 四川大学 High-flexibility melamino-formaldehyde foam material and preparation method thereof
CN103665755A (en) * 2013-11-28 2014-03-26 南通紫鑫实业有限公司 Preparation methods of melamino-formaldehyde resin for foam and melamino-formaldehyde resin foam
CN103665755B (en) * 2013-11-28 2015-09-30 南通紫鑫实业有限公司 The preparation method of melamine formaldehyde resin for foam, terpolycyantoamino-formaldehyde resin foam

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